Tantalum based alloy that is resistant to aqueous corrosion

ABSTRACT

A tantalum or tantalum alloy which contains pure or substantially pure tantalum and at least one metal element selected from the group consisting of Ru, Rh, Pd, Os, Ir, Pt, Mo, W and Re to form a tantalum alloy that is resistant to aqueous corrosion. The invention also relates to the process of preparing the tantalum alloy.

RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/540,215, filed Aug. 14, 2019, which is a continuation of U.S. patentapplication Ser. No. 15/928,187, filed Mar. 22, 2018, which is acontinuation of U.S. patent application Ser. No. 15/643,980, filed Jul.7, 2017, which is a continuation of U.S. patent application Ser. No.12/109,765, filed Apr. 25, 2008, which claims the benefit of andpriority to U.S. Provisional Patent Application No. 60/914,474, filedApr. 27, 2007, the entire disclosure of each of which is herebyincorporated herein by reference.

FIELD OF THE INVENTION

The invention is directed to tantalum or tantalum based alloys that areresistant to aqueous corrosion, more particularly to corrosion fromacids and resistant to hydrogen embrittlement. The tantalum or tantalumbased alloy has superior resistance to hydrogen absorption (andsubsequent hydrogen embrittlement) as compared to pure tantalum andTa-3W (referred to as “NRC76”).

BACKGROUND OF THE INVENTION

Pure tantalum and tantalum alloys begin to become significantly hydrogenembrittled at hydrogen concentrations greater than 100 ppm. In thechemical processing industry (CPI), pure tantalum will absorb hydrogenand become embrittled when exposed to hot HCl and hot H₂SO₄ atconditions illustrated in FIGS. 2 and 3. Ta-3W has demonstrated betterresistance to hydrogen absorption than pure tantalum. Where tantalum andtantalum alloys are used in the CPI to contain very hot and concentratedacids, hydrogen embrittlement, rather than a loss of wall thickness dueto corrosion, is the predominant failure mechanism.

U.S. Pat. No. 4,784,830 discloses that oxidation resistance of alloyscan be improved by a controlled addition and retention of nitrogen. Putanother way, it has been discovered that the microstructure of thealloys of the type under consideration, notably grain size, can becontrolled or rendered relatively structurally stable over extendedperiods at elevated temperature through a microalloying addition ofnitrogen. In addition, and most advantageously, a special ratio ofsilicon to titanium should be observed in seeking extended service lifeas will be shown herein.

U.S. Pat. No. 3,592,639 relates to a ternary Ta—W alloy which containsfrom 1.5 to 3.5 percent of tungsten. Niobium can also be present in thealloy from 0.05 to 0.5 weight percent. Molybdenum is limited to 0.5%maximum (less than 5000 p.p.m.) to promote smaller grain size in thealloy.

U.S. Pat. No. 4,062,679 claims a wrought tantalum product of,substantially pure tantalum containing less than 300 parts per millionof columbium, less than 200 parts per million of iron, chromium andnickel combined, less than 50 parts per million of tungsten, less than10 parts per million of molybdenum, less than 30 parts per million ofchromium, and less than 20 parts per million of calcium, the improvementwhich comprises the inclusion of from about 50 to about 700 parts permillion of silicon in the composition of said product whereby saidproduct is improved in resistance to embrittlement when exposed toelevated temperatures in an oxygen-containing environment.

SUMMARY OF THE INVENTION

The invention relates to a process of improving hydrogen embrittlementresistance by microalloying at least one metal element selected from thegroup consisting of Ru, Rh Pd, Os, Ir, Pt, Mo, W and Re with a pure orsubstantially pure tantalum or a tantalum alloy.

One preferred embodiment of this invention would add platinum to NRC76.The chemical process industry is seeking new tantalum alloys that willpermit greater operating temperatures in their process equipment.

An object of the invention is to have an improved tantalum alloy whichis more resistant to aqueous corrosion and hydrogen embrittlement.

A tantalum alloy which comprises pure or substantially pure tantalum ora tantalum alloy and at least one metal element selected from the groupconsisting of Ru, Rh Pd, Os, Ir, Pt, Mo, W and Re to form a tantalumalloy that is resistant to aqueous corrosion.

The metal element(s) can be in an amount up to the solubility limit ofmetal in the tantalum.

BRIEF DESCRIPTION OF THE FIGURES

FIGS. 1A-1C are phase diagrams for Ta—W (FIG. 1A), Ta—Mo (FIG. 1B), andMo—W (FIG. 1C) that illustrate the addition of molybdenum since it hasthe same crystal structure, a similar lattice parameter, and completesolid solubility in both tantalum and tungsten.

FIG. 2 illustrates the conditions for the chemical processing industrythat pure tantalum will absorb hydrogen and become embrittled whenexposed to hot HCl.

FIG. 3 illustrates the conditions for the chemical processing industrythat pure tantalum will absorb hydrogen and become embrittled whenexposed to hot H₂SO₄.

FIGS. 4A and 4B illustrate the results for corrosion rate (FIG. 4A) andhydrogen enrichment (FIG. 4B) after short term corrosion tests inhydrochloric acid.

FIGS. 5A and 5B illustrate the results for corrosion rate (FIG. 5A) andhydrogen enrichment (FIG. 5B) after long term corrosion tests inhydrochloric acid.

FIGS. 6A and 6B illustrate the results for corrosion rate (FIG. 6A) andhydrogen enrichment (FIG. 6B) after long term corrosion tests in sulfuracid.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, the singular terms “a” and “the” are synonymous and usedinterchangeably with “one or more.” Accordingly, for example, referenceto “a metal” herein or in the appended claims can refer to a singlemetal or more than one metal. Additionally, all numerical values, unlessotherwise specifically noted, are understood to be modified by the word“about.”

A tantalum or tantalum based alloy that is resistant to aqueouscorrosion, more particularly to corrosion from acids and resistant tohydrogen embrittlement. The starting tantalum is pure or substantiallypure. Substantially pure tantalum would be a tantalum alloy which has upto about 11% by weight of non-tantalum components.

The tantalum or tantalum based alloys are preferably prepared using avacuum melting process. Vacuum arc remelting (VAR), electron beammelting (EBM) or plasma arc melting (PAM) are methods of vacuum meltingthat can also be used for alloying. To formulate the actual alloy, atleast one element selected from the group consisting of ruthenium,rhodium, palladium, osmium, iridium, platinum, molybdenum, tungsten, andruthenium (Ru, Rh Pd, Os, Ir, Pt, Mo, W and Re) are added to the puretantalum material or substantially pure tantalum material or tantalumalloy using one of the vacuum melting processes listed above. Thetantalum alloy preferably contains tungsten with platinum, molybdenum orrhenium or mixtures thereof. Although it is noted that VAR, EBM or PAMcould all be used. The preferred technique would be VAR.

Alternative embodiments of this invention could include adding elementsother than the elements listed above that improve the corrosion andhydrogen embrittlement resistance. These additional elements couldinclude yttrium, gold, cerium, praseodymium, neodymium, and thorium.

Each of the metals would preferably be less than 10,000 ppm of thealloy, preferably less than 5,000 ppm of the total amount of the alloyand more preferably less 2,000 ppm of the total amount of alloy. Themetal preferably would be added in an amount of at least 50 ppm,preferably at least 100 ppm, preferably at least 150 ppm, preferably atleast 200 ppm and preferably at least 250 ppm.

Examples of tantalum alloys that contain at least 89% tantalum include,but are not limited to Ta-3W (tantalum-tungsten) contains at about 3%tungsten), Ta-3W—Pt (tantalum-tungsten and platinum alloy) whichcontains about 3% tungsten), the tantalum Ta-3W—Mo (tantalum-tungstenand molybdenum alloy) which contains about 3% tungsten), and Ta-3W—Realloys (tantalum-tungsten and rhenium alloy) which contains about 3%tungsten). The Ta-3W—Pt, Ta-3W—Mo and Ta-3W—Re would be formulated andmanufactured in a manner similar that used to make Ta-3W alloys. Thealloys are preferably made by microalloying the other metals with theTa-3W (tantalum-tungsten) alloy.

The addition of platinum would be the most preferred embodiment sinceplatinum has the greatest number of free electrons to theoretically pullin additional oxygen atoms to close the holes in the Ta₂O₅ oxide layerand/or provide sites of low hydrogen overvoltage thereby stabilizing theTa₂O₅ oxide layer.

Another preferred embodiment would use the addition of ruthenium,rhodium, palladium, osmium, and iridium (also known as “platinum groupmetals, PGM) which also would provide sites of low hydrogen overvoltagethereby stabilizing the Ta₂O₅ oxide layer.

Still another preferred embodiment would use the addition of molybdenumsince it has the same crystal structure, a similar lattice parameter,and complete solid solubility in both tantalum and tungsten. This isshown in Table I and FIGS. 1A-1C.

TABLE I Crystal Structure and Lattice Parameters for Refractory ElementsLattice Parameter Element Symbol Crystal Structure (Å) Tantalum Ta bodycentered cubic (bcc) 3.296 Tungsten W body centered cubic (bcc) 3.16Molybdenum Mo body centered cubic (bcc) 3.15 Platinum Pt face centeredcubic (fcc) 3.931 Rhenium Re hexagonal close packed (hcp) a = 2.761, c =4.458

Another preferred embodiment would use the addition of rhenium sincerhenium has the same crystal structure and a similar lattice parameterto tantalum and tungsten.

Tantalum ingots formulated using VAR or PAM would then be used toproduce plate, sheet, and tube products in a manner similar to that usedto manufacture these same products from pure tantalum or Ta-3W alloy.

The plate, sheet, and tube products manufactured using the Ta-3W—Mo,Ta-3W—Re, or Ta-3W—Pt alloys would be used in a manner identical to thatfor from pure tantalum or Ta-3W alloys.

The advantages of the new alloys would be superior corrosion andhydrogen embrittlement resistance over pure Ta-3W. The addition ofplatinum would be the preferred embodiment since platinum has thegreatest number of free electrons to theoretically pull in additionaloxygen atoms and help close the holes in the Ta₂O₅ oxide layer and/orprovide sites of low hydrogen overvoltage thereby stabilizing the Ta₂O₅oxide layer.

Samples were made using either a laser additive manufacturing (LAM) ortraditional vacuum arc remelting (VAR) techniques. In the formertechnique, tantalum, tungsten, and platinum powders were blendedtogether in the desire composition and then melted using andconsolidated using a laser under inert conditions. In these samples, thefinal tantalum alloy contained 2.8 weight percent tungsten with 500 ppmplatinum. In the latter technique, tantalum and platinum powders wereblended together in the desire composition, pressed into a powder leech,and welded to the side of an NRC76 bar (this assembly herein referred toas the “electrode”). The electrode was then melted using traditionalvacuum arc remelting (VAR) techniques. In these samples, the finaltantalum alloy contained 2.8 weight percent tungsten with up to 10,000ppm platinum.

Corrosion tests in hydrochloric and sulfuric acids were conducted for upto a four month time period. The platinum modified alloy had a corrosionrate that was always lower than NRC76 with almost no hydrogenenrichment.

FIGS. 4A and 4B show the results for short term corrosion tests inhydrochloric acid. The platinum containing alloys have a significantlylower corrosion rate than the NRC76 alloy. This corrosion rate isreduced from approximately 16 mils per year (mpy) for NRC76 to less than4 mpy when platinum concentrations exceed approximately 1000 ppm. Inaddition, the hydrogen concentration after testing has dropped from 291ppm to less than 4 ppm when platinum concentrations are betweenapproximately 1000 ppm to 10,000 ppm.

FIGS. 5A and 5B show the results for long term corrosion tests inhydrochloric acid. The platinum containing alloys had a corrosion ratethat was three times lower than the NRC76 alloy when platinumconcentrations exceed approximately 1000 ppm. In addition, the hydrogenconcentration after testing has dropped from 756 ppm to less than 10 ppmwhen platinum concentrations were greater than approximately 1000 ppm.

FIGS. 6A and 6B show the results for long term corrosion tests insulfuric acid. The platinum containing alloys have a significantly lowercorrosion rate than the NRC76 alloy. This corrosion rate is reduced fromapproximately 9.2 mils per year (mpy) for NRC76 to less than 4 mpy whenplatinum concentrations exceed approximately 1500 ppm. In addition, thehydrogen concentration after testing has dropped from 9 ppm to less than2 ppm when platinum concentrations were greater than approximately 1000ppm.

All the references described above are incorporated by reference in itsentirety for all useful purposes.

While there is shown and described certain specific structures embodyingthe invention, it will be manifest to those skilled in the art thatvarious modifications and rearrangements of the parts may be madewithout departing from the spirit and scope of the underlying inventiveconcept and that the same is not limited to the particular forms hereinshown and described.

1.-22. (canceled)
 23. A method of producing a tantalum alloy that isresistant to aqueous corrosion, the method comprising microalloying pureor substantially pure tantalum with Mo, wherein (i) the microalloying isperformed to produce the tantalum alloy via laser additive manufacturing(LAM), vacuum arc remelting (VAR), electron beam melting (EBM), orplasma arc melting (PAM), and (ii) the Mo is present, in the tantalumalloy, in an amount less than its solubility limit in the pure orsubstantially pure tantalum.
 24. The method of claim 23, wherein the Mois present in an amount of at least 250 ppm in the tantalum alloy. 25.The method of claim 23, wherein (i) substantially pure tantalum ismicroalloyed with the Mo, and (ii) the substantially pure tantalumcomprises Ta-3W.
 26. The method of claim 23, wherein the microalloyingis performed via laser additive manufacturing (LAM).
 27. The method ofclaim 23, wherein the microalloying is performed via vacuum arcremelting (VAR).
 28. The method of claim 23, wherein the microalloyingis performed via electron beam melting (EBM).
 29. The method of claim23, wherein the microalloying is performed via plasma arc melting (PAM).30. The method of claim 23, wherein, after the microalloying, thetantalum alloy consists essentially of pure tantalum and Mo.
 31. Themethod of claim 23, wherein, after the microalloying, the tantalum alloyconsists of pure tantalum and Mo.
 32. The method of claim 23, wherein,after the microalloying, the tantalum alloy consists of substantiallypure tantalum and Mo, the substantially pure tantalum containing no morethan 11% by weight of non-tantalum components.
 33. The method of claim23, wherein the Mo is present in an amount of at most 10,000 ppm in thetantalum alloy.
 34. The method of claim 23, wherein the Mo is present inan amount of at most 5,000 ppm in the tantalum alloy.
 35. The method ofclaim 23, wherein the Mo is present in an amount of at most 2,000 ppm inthe tantalum alloy.
 36. The method of claim 23, wherein the Mo ispresent in an amount of at least 50 ppm in the tantalum alloy.
 37. Themethod of claim 23, wherein the Mo is present in an amount of at least500 ppm in the tantalum alloy.
 38. A tantalum alloy resistant to aqueouscorrosion and consisting essentially of Ta-3W-Mo, wherein Mo is presentin an amount of at least 50 ppm and at most 10,000 ppm.
 39. The tantalumalloy of claim 38, wherein Mo is present in an amount of at least 500ppm and at most 10,000 ppm.
 40. The tantalum alloy of claim 38, whereinMo is present in an amount of at least 500 ppm and at most 5,000 ppm.41. The tantalum alloy of claim 38, wherein Mo is present in an amountof at least 500 ppm and at most 2,000 ppm.